JP5636099B2 - Zinc-manganese silicate light-emitting material containing metal particles and preparation method thereof - Google Patents

Description

  The present invention relates to a light emitting material and a method for preparing the same, and more particularly to a manganese-doped zinc silicate green light emitting material containing metal particles and a method for preparing the same.

  In recent years, field emission devices have attracted attention because they have advantages such as low operating voltage, low energy consumption, no need for polarizing coils, no X-ray radiation, anti-radiation and magnetic field interference. The combination of the light emitting material and the light emitting material can provide a field emission light source with high brightness and color rendering, and can be applied to fields such as display, various instructions, and ordinary illumination.

  One of the important factors in producing a field emission device with excellent performance is the preparation of high-performance fluorescent powder. Fluorescent materials currently used in field emission devices are mainly sulfide-based, oxide-based and sulfur oxide-based fluorescent powders used in conventional cathode ray tubes and projection television kinescopes. For example, Chinese Patent No. 200410025310.5 disclosed a method for preparing manganese-doped zinc silicate green fluorescent powder by low temperature solid state reaction. In this method, mesoporous silicon dioxide, zinc salt, and manganic salt are used as raw materials, and accurately weighed mesoporous silicon oxide is dispersed in an alcohol solution of zinc salt and manganic salt, dried, and then neutralized. Under protection, it is calcined at 750 ° C. to 950 ° C. and subjected to solid phase reaction to prepare manganese-doped zinc silicate high-efficiency green fluorescent powder. Manganese-doped zinc silicate prepared by this method has high color purity but not high luminous efficiency.

  The technical problem to be solved by the present invention is to provide a metal particle-containing zinc ion-doped zinc silicate green light emitting material having good stability and high emission intensity, and a method for preparing the same.

Technical means for solving the technical problem of the present invention, containing metal particles, providing manganese ions doped zinc silicate green light emitting material, its chemical formula _{Zn 2-x SiO 4: Mn} x, be M _y In the formula, M is a metal, the range of x value is 0.001 ≦ x ≦ 0.1, and the range of y value is 0.00001 ≦ y ≦ 0.01.

  In the light emitting material of the present invention, the metal M is one of Ag, Au, and Pt. The x value range is 0.001 ≦ x ≦ 0.08, and the y value range is 0.00001 ≦ y ≦ 0.005.

In addition, a method for preparing a metal ion-containing, zinc ion-doped zinc silicate green light emitting material is provided,
Preparing a silica aerogel containing metal particles, step 1;
Based on the stoichiometric ratio, the zinc ion source compound, the manganese ion source compound, and the metal particle-containing silica aerogel of step 1 are weighed and mixed to obtain a mixture, stoichiometry formula _{Zn 2-x} SiO ₄ of the compound to each _source: Mn x, based on the molar ratio of the element corresponding in _{M y,} wherein, M is a metal, the range of x values 0 Step 2 in which .001 ≦ x ≦ 0.1 and the range of y values is 0.00001 ≦ y ≦ 0.01;
And step 3 of obtaining the zinc ion-doped zinc silicate green light emitting material containing the metal particles after heat-sintering, cooling and polishing the mixture in step 2.

In the method of the present invention, the step of preparing the silica aerogel containing metal particles in the step 1 includes first adding the weighed silica aerogel to an ethanol solution containing a corresponding compound of metal, and The mixture is stirred at 0.5 ° C. for 3 to 3 hours, then sonicated for 10 minutes, further dried at 60 ° C. to 150 ° C., the dried raw material is polished, Baking for 5 hours to 3 hours. The metal particles are one of metals Ag, Au, and Pt, the corresponding compound of Ag is silver nitrate, the corresponding compound of Au is HAuCl ₄ , and the corresponding compound of Pt is HPtCl ₄ .

  In step 2, the zinc ion source compound is one of zinc oxide, zinc nitrate, zinc acetate, and zinc oxalate, and the manganese ion source compound is manganese oxide, manganese acetate, manganese carbonate. , And one of manganese oxalate.

  In step 3, the sintering temperature is 1000 ° C. to 1400 ° C., the sintering time is 1 hour to 10 hours, and the heat insulation sintering is performed in an air atmosphere.

Compared with the prior art, in the present invention, the manganese ion-doped zinc silicate green light-emitting material containing metal particles is added with a metal element, so that under the excitation of the cathode ray, the metal has a Zn ₂ SiO ₄ : Mn interface. A surface plasmon effect was generated, and this effect effectively improved the light emission performance of Zn ₂ SiO ₄ : Mn, thereby increasing the light emission luminance of the light emitting material of the present invention. In addition, the preparation method of the present invention has simple steps, is easy to operate, has a low firing temperature, and is low in cost.

3 is a flow sheet of a method for preparing a manganese ion-doped zinc silicate green light emitting material containing metal particles of the present invention. Example metal particles containing prepared by 4 of the present invention, manganese ions doped zinc silicate green light emitting material and the _Zn 1.992 _{SiO 4:} a cathodoluminescence spectrum comparison diagram between _{Mn 0.008} luminescent material. The cathode ray emission spectrum was analyzed using a Shimadzu RF-5301PC spectrum device as a detector under excitation of a cathode ray at a 5 KV acceleration voltage.

  In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in more detail with reference to the drawings and examples. It should be understood that the specific embodiments described herein are only used to interpret the present invention and are not intended to limit the present invention.

The present invention, containing metal particles, providing manganese ions doped zinc silicate green light emitting material, its chemical formula _{Zn 2-x} SiO _4: a Mn x, _{M y,} wherein, M is a metal, x The value range is 0.001 ≦ x ≦ 0.1, and the y value range is 0.00001 ≦ y ≦ 0.01.

  In the light emitting material of the present invention, the metal M is one of Ag, Au, and Pt. The x value range is 0.001 ≦ x ≦ 0.08, and the y value range is 0.00001 ≦ y ≦ 0.005.

FIG. 1 shows a flow sheet of the preparation method of the present invention,
Preparing a silica aerogel containing metal particles, having a pore size of 20 nm to 100 nm and a porosity of 92% to 98%;
Based on the stoichiometric ratio, the zinc ion source compound, the manganese ion source compound, and the metal particle-containing silica airgel of step S01 are weighed and mixed to obtain a mixture, stoichiometry formula _{Zn 2-x} SiO ₄ of the compound to each _source: Mn x, based on the molar ratio of the element corresponding in _{M y,} wherein, M is a metal, the range of x values 0 Step S02 in which .001 ≦ x ≦ 0.1 and the y value range is 0.00001 ≦ y ≦ 0.01;
And step S03 of obtaining a zinc ion-doped zinc silicate green light emitting material containing the metal particles after the mixture in step S02 is heated and sintered in an air atmosphere, cooled to room temperature and polished.

In the method of the present invention, in the step of preparing the silica aerogel containing metal particles in the step S01, first, the weighed silica aerogel is added to an ethanol solution containing a corresponding compound of metal, and 50 ° C to 75 ° C. The mixture is stirred at 0.5 ° C. for 3 to 3 hours, then sonicated for 10 minutes, further dried at 60 ° C. to 150 ° C., the dried raw material is polished, Calcination for 5 to 3 hours. The metal particles are one of metals Ag, Au, and Pt, the corresponding compound of Ag is silver nitrate, the corresponding compound of Au is HAuCl ₄ , and the corresponding compound of Pt is HPtCl ₄ .

  In step S02, the zinc ion source compound is one of zinc oxide, zinc nitrate, zinc acetate, and zinc oxalate, and the manganese ion source compound is manganese oxide, manganese acetate, carbonic acid. One of manganese and manganese oxalate.

  In step S03, the sintering temperature is 1000 ° C. to 1400 ° C., and the sintering time is 1 hour to 10 hours.

The zinc silicate green light-emitting material containing metal particles and doped with manganese ions according to the present invention contains a metal element, so that noble metal Ag, Au, or Pt has a Zn ₂ SiO ₄ : Mn interface under the excitation of a cathode ray. A surface plasmon effect was generated, and this effect increased the light emission brightness of the light emitting material of the present invention by effectively improving the light emission performance of Zn ₂ SiO ₄ : Mn. In addition, the preparation method of the present invention has simple steps, is easy to operate, has a low firing temperature, and is low in cost.

  Hereinafter, different preparation methods and other features of the zinc silicate green light emitting material containing metal particles and doped with manganese ions according to the present invention will be described through a plurality of examples.

Example 1 Preparation of Zn _1.999 SiO ₄ : Mn _0.001 , Au _0.00001 green light emitting material First, silica _airgel 0.3 was weighed and 10 ml of 0.5 × 10 ⁻⁵ mol / The sample was added to an ethanol solution containing L chloroauric acid (HAuCl ₄ ), stirred at 50 ° C. for 3 hours, then sonicated for 10 minutes, further dried at a temperature of 60 ° C., and the dried sample was Polish and homogenize, pre-fire at 600 ° C. for 4 hours, then weigh 1.5144 g of zinc nitrate, 0.0005 g of manganese carbonate and 0.2404 g of silica airgel containing gold (Au) and mix uniformly. , and 10 hours calcined kept under 1000 ° C. in air, and then cooled to room _temperature, Zn 1.999 _{SiO 4:} obtained Mn _0.001, the _{Au 0.00001} new green light emitting material . This luminescent material can emit green light under the excitation of a cathode ray, has good luminescent performance and high color purity.

Example 2 Preparation of Zn _1.94 SiO ₄ : Mn _0.06 , Ag _0.001 green light emitting material First, silica airgel 1.0 was weighed and 30 ml of 5.43 × 10 ⁻⁴ mol / LAgNO. ₃ and dissolved in an ethanol solution containing _{3 and} stirred at 70 ° C. for 0.5 hour, then sonicated for 10 minutes, further dried at 150 ° C., and the dried sample was polished and homogenized. Pre-baking at 1000 ° C. for 0.5 hour. Then zinc oxalate _{(ZnC 2} O 4) _1.1904g, manganese oxalate _{(MnC 2} O 4) were uniformly mixed and weighed silica airgel 0.2404g of 0.0343g and Ag-containing, 1200 ° C. in air Then, the mixture is _heated and held for 6 hours and then cooled to room temperature to obtain a Zn _1.94 SiO ₄ : Mn _0.06 , Ag _0.001 new green light emitting material. This material can emit green light under the excitation of a cathode ray, has good light emission performance and high color purity.

Example 3 Preparation of Zn _1.92 SiO ₄ : Mn _0.08 , Pt _0.005 green light emitting material First, silica airgel 1.0 was weighed and 30 ml of 2.72 × 10 ⁻³ mol / LHPtCl. ₄ dissolved in ethanol solution, stirred at 70 ° C. for 0.5 hour, then sonicated for 10 minutes, further dried at 150 ° C., the dried sample was polished and homogenized, Pre-baking at 1000 ° C. for 0.5 hour. Thereafter, 1.4093 g of zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), 0.0554 g of manganese acetate (Mn (CH ₃ CO ₂ ) ₂ ), and 0.2404 g of Pt-containing silica airgel were weighed uniformly. And the mixture is calcined at 1300 ° C. for 4 hours. Thereafter, it is cooled to room temperature to obtain a Zn _1.92 SiO ₄ : Mn _0.08 , Pt _0.005 new green light emitting material. This material can emit green light under the excitation of a cathode ray, has good light emitting performance, and high color purity.

Example 4 Preparation of Zn _1.992 SiO ₄ : Mn _0.008 , Ag _0.0007 green light emitting material First, silica airgel 0.4 was weighed and 15 ml of 3.13 × 10 ⁻⁴ mol / LAgNO. ₃ and dissolved in an ethanol solution containing _{3 and} stirred at 60 ° C. for 1.5 hours, then sonicated for 10 minutes, further dried under 70 ° C., and the dried sample was polished and homogenized. Pre-bake at 800 ° C. for 2 hours. Thereafter, 0.6486 g of zinc oxide (ZnO), 0.0037 g of manganese carbonate (MnCO ₃ ), and 0.2404 g of Ag-containing silica airgel after firing were weighed and mixed uniformly, and the mixture was air-treated at 1250 ° C. for 4 hours. Keep fired. Then cooled to room _{temperature, Zn 1.992 SiO 4: Mn 0.008} , obtaining _{Ag 0.0007} new green luminescent material. This material can emit green light under the excitation of a cathode ray, has good light emission performance and high color purity.

FIG. 2 is a cathode ray emission spectrum contrast diagram of the Zn _1.992 SiO ₄ : Mn _0.008 luminescent material and the silicate luminescent material prepared according to Example 4, and the curve 10 is prepared according to Example 4. The silicate luminescent material is shown, and the curve 11 indicates the Zn _1.992 SiO ₄ : Mn _0.008 luminescent material. As can be seen from FIG. 2, the luminescence intensity of the luminescent material prepared according to Example 4 exceeded 50% of the Zn _1.992 SiO ₄ : Mn _0.008 fluorescent powder that was not Ag-doped. The light-emitting material prepared according to Example 4 is characterized by good stability and high luminous efficiency.

Example 5 Preparation of Zn _1.9 SiO ₄ : Mn _0.1 , Au _0.01 green light emitting material First, silica airgel 1.0 was weighed and 30 ml of 5.43 × 10 ⁻³ mol / LHAuCl. Dissolve in ethanol solution containing _{4 and} stir at 70 ° C. for 0.5 hour. The sample was then sonicated for 10 minutes, further dried under conditions of 150 ° C., the dried sample was polished to be uniform, pre-fired at 1400 ° C. for 1 hour, and then zinc oxide (ZnO) 0.6186 g, Manganese oxide (MnO) 0.0284 g and Au-containing silica airgel 0.2404 g are weighed and mixed uniformly, and the mixture is baked and kept at 1200 ° C. for 4 hours in air. Thereafter, it is cooled to room temperature to obtain a Zn _1.9 SiO ₄ : Mn _0.1 , Au _0.01 new green light emitting material. This material can emit green light under the excitation of a cathode ray, has good light emission performance and high color purity.

  The embodiments described above are merely preferred embodiments of the present invention and do not limit the present invention. Any modifications, equivalent changes and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

In a zinc ion silicate green light emitting material doped with manganese ions, containing metal particles,
The metal particle-containing chemical formula of the manganese ions doped zinc silicate green light emitting material _{Zn 2-x SiO 4: Mn} x, a _{M y,} wherein, M is Ag, Au, In one of Pt Silicic acid containing metal particles and doped with manganese ions, wherein x value range is 0.001 ≦ x ≦ 0.1 and y value range is 0.00001 ≦ y ≦ 0.01 Zinc green light emitting material.   2. The manganese-containing metal particle according to claim 1, wherein the x value range is 0.001 ≦ x ≦ 0.08 and the y value range is 0.00001 ≦ y ≦ 0.005. 3. Ion-doped zinc silicate green light emitting material. A method for preparing a manganese ion-doped zinc silicate green light emitting material containing metal particles,
Preparing a silica aerogel containing metal particles, step 1;
Based on the stoichiometric ratio, the zinc ion source compound, the manganese ion source compound, and the metal particle-containing silica aerogel of step 1 are weighed and mixed to obtain a mixture, stoichiometry formula _{Zn 2-x} SiO ₄ of the compound to each _source: Mn x, based on the molar ratio of the element corresponding in _{M y,} wherein, M is Ag, Au, of Pt 1 in seeds, the range of x values is 0.001 ≦ x ≦ 0.1, and step 2 range of y values is 0.00001 ≦ y ≦ 0.01,
Step 3 to obtain a zinc ion-doped zinc silicate green light-emitting material containing the metal particles after heat-sintering, cooling and polishing the mixture in Step 2;
A method for preparing a zinc silicate green light-emitting material containing metal particles and doped with manganese ions. In the step of preparing the silica aerogel containing metal particles in the step 1, first, the weighed silica aerogel is added to an ethanol solution containing a corresponding compound of metal, and 0.5 to 50 ° C. to 75 ° C. Stirred for 3 hours, then sonicated for 10 minutes, further dried at 60 ° C to 150 ° C, polished raw material, then fired at 600 ° C to 1300 ° C for 0.5 hours to 3 hours The method for preparing a zinc silicate green light emitting material doped with manganese ions and containing metal particles according to claim 3 , wherein the method comprises the step of: The metal ion according to claim 3 , wherein the corresponding compound of Ag is silver nitrate, the corresponding compound of Au is HAuCl ₄ , and the corresponding compound of Pt is HPtCl _4. Method for preparing doped zinc silicate green light emitting material. In step 2, the zinc ion source compound is one of zinc oxide, zinc nitrate, zinc acetate, and zinc oxalate, and the manganese ion source compound is manganese oxide, manganese acetate, manganese carbonate. The method for preparing a zinc silicate green light-emitting material doped with manganese ions and containing metal particles according to claim 3 , wherein the material is one of manganese oxalate and manganese oxalate. In step 3, the sintering temperature is 1000 ° C. to 1400 ° C., and wherein the sintering time is 1 hour to 10 hours, is manganese ion doping contain metal particles as claimed in claim 3 silicate Preparation method of zinc green light emitting material. In Step 3, characterized in that the thermal insulation sintering is performed in an air atmosphere, a process for the preparation of zinc silicate green light emitting material is manganese ion doping contain metal particles according to claim 3.